JP7240586B2 - Resin composition, resin sheet, multilayer printed wiring board and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, a resin sheet using the same, a multilayer printed wiring board and a semiconductor device.

2. Description of the Related Art With the miniaturization and high density of multilayer printed wiring boards, efforts are being actively made to reduce the thickness of laminates used in multilayer printed wiring boards. Along with the reduction in thickness, the insulation layer is also required to be thinner, and a resin sheet containing no glass cloth is required. The resin composition used as the material of the insulating layer is mainly a thermosetting resin, and holes for obtaining electrical connection between the insulating layers are generally made by laser processing.

On the other hand, drilling by laser processing has a problem that the processing time becomes longer as the number of holes increases in a high-density substrate. Therefore, in recent years, by using a resin composition that allows the exposed area to be cured (exposure process) and the unexposed area to be removed (development process) by irradiation with light, etc., it is possible to perform batch drilling in the exposure and development processes. There is a demand for a resin sheet that makes this possible.

As a method of exposure, a method of exposing through a photomask using a mercury lamp as a light source is used. In recent years, as an exposure method, a direct drawing exposure method has been introduced in which a pattern is directly drawn on a photosensitive resin composition layer without using a photomask based on digital data of a pattern. This direct writing exposure method has better alignment accuracy than the exposure method using a photomask, and can obtain highly detailed patterns. I'm in. A monochromatic light such as a laser is used as a light source, and a light source with a wavelength of 405 nm (h-line) is used in a DMD (Digital Micromirror Device) type apparatus capable of forming a high-definition resist pattern.

A compound having an ethylenically unsaturated group such as (meth)acrylate is used in a photosensitive resin composition used for laminates and resin sheets in order to enable rapid curing in an exposure process.
For example, in Patent Document 1, a carboxyl-modified epoxy (meth)acrylate resin obtained by reacting a bisphenol-type epoxy resin and (meth)acrylic acid and then reacting an acid anhydride, a biphenyl-type epoxy resin, A photosensitive thermosetting resin composition is described that includes a photoinitiator and a diluent.

Further, in Patent Document 2, a photocurable binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization (curing) initiator, a sensitizer, and a heat curing agent bisallyl nagic A resin composition is described that includes an imide compound and a bismaleimide compound.

Patent Document 3 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent).

Japanese Patent Application Laid-Open No. 2005-62450 Japanese Patent Application Laid-Open No. 2010-204298 WO2018/56466A1

However, a cured product using a conventional (meth)acrylate resin does not have sufficient physical properties, and there is a limit to the formation of a highly heat-resistant protective film and an interlayer insulating layer.

The cured product obtained from the resin composition described in Patent Document 1 is described as having excellent flexibility and folding resistance as a solder resist, and is also excellent in heat resistance. There is no specific value for , and there is a problem that it is inferior in heat resistance and thermal stability to use as an interlayer insulating layer.

Although Patent Document 2 describes the use of a bismaleimide compound, it is described as a thermosetting agent, and (meth)acrylate is used as the photopolymerizable compound. Therefore, there is a problem that it is inferior in heat resistance and thermal stability when used as an interlayer insulating layer.

In Patent Document 3, a bismaleimide compound is used as the curable resin. However, since the maleimide compound has poor light transmittance, when the maleimide compound is included, the light does not sufficiently reach the photocuring initiator, and the photocuring initiator does not reach the photocuring initiator. is difficult to generate radicals and its reactivity is very low. Therefore, in Patent Document 3, the maleimide compound is cured by performing additional heating before development. Patent Document 3 does not describe at all about using an active energy ray containing a wavelength of 405 nm (h-line) as a light source capable of irradiation.

Therefore, the present invention has been made in view of the above problems, and when exposed to an active energy ray containing a wavelength of 405 nm (h-line), it can be photo-cured, and in particular a multilayer printed wiring board The object of the present invention is to provide a resin composition which is excellent in photocurability, heat resistance and thermal stability when used in a resin composition, a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device.

The present inventors found that by using a resin composition containing a specific maleimide compound (A) and a photocuring initiator (B) having an absorbance of 0.1 or more at a wavelength of 405 nm (h-line), The inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing a maleimide compound (A) represented by the following general formula (1) and a photocuring initiator (B) having an absorbance of 0.1 or more at a wavelength of 405 nm (h-line) .

In formula (1), the number of n is 1 or more.

[2] The content of the maleimide compound (A) is 50 to 99.9 parts by mass with respect to a total of 100 parts by mass of the maleimide compound (A) and the photocuring initiator (B), [1 ] The resin composition as described in .
[3] The resin composition according to [1] or [2], wherein the photocuring initiator (B) is a compound represented by the following general formula (2).

In formula (2) , each R ₁ independently represents a substituent represented by the following general formula (3) or a phenyl group.

In formula (3), -* represents a bond, and each R ₂ independently represents a hydrogen atom or a methyl group.

[4] having a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains the resin composition according to any one of [1] to [3]; resin sheet.
[5] The resin sheet according to [4], wherein the resin layer has a thickness of 1 to 50 μm.
[6] A multilayer printed wiring board comprising the resin composition according to any one of [1] to [5].
[7] A semiconductor device comprising the resin composition according to any one of [1] to [5].

According to the present invention, when exposed to an active energy ray containing a wavelength of 405 nm (h-line), it can be photosensitized and photocured. A resin composition having excellent thermal stability, a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

In this specification, "(meth)acryloyl group" means both "acryloyl group" and corresponding "methacryloyl group", and "(meth)acrylate" means "acrylate" and corresponding "methacrylate and "(meth)acrylic acid" means both "acrylic acid" and the corresponding "methacrylic acid". Further, in the present embodiment, unless otherwise specified, the "resin solid content" or "resin solid content in the resin composition" refers to the photocuring initiator (B), additives, solvents and The component excluding the filler, and "100 parts by mass of resin solid content" means that the total of the components excluding the photocuring initiator (B), the additive, the solvent and the filler in the resin composition is 100 parts by mass. It shall be said that

The resin composition of the present embodiment comprises a maleimide compound (A) represented by the general formula (1) and a photocuring initiator (B) having an absorbance of 0.1 or more at a wavelength of 405 nm (h-line). Contains the containing resin composition. Each component will be described below.

<Maleimide compound (A) represented by general formula (1)>
The maleimide compound (A) (also referred to as component (A)) according to the present embodiment has the structure of general formula (1).
Generally, maleimide compounds have poor light transmittance, so when a resin composition contains a maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, causing the photocuring initiator to generate radicals. unlikely to occur. Therefore, the radical photoreaction of maleimide is generally difficult to proceed, and even if the radical polymerization or dimerization reaction of maleimide alone proceeds, the reactivity is very low. However, the maleimide compound (A) according to the present embodiment can be obtained by preparing a chloroform solution containing 0.01% by mass of the maleimide compound (A) and using a light beam with a wavelength of 405 nm (h-line). When the transmittance is measured, the transmittance is 1% or more, showing very excellent light transmittance, so that the photoradical reaction of maleimide tends to occur efficiently.
The light transmittance is preferably 2% or more, more preferably 4% or more, because a resin composition having excellent photocurability, heat resistance and thermal stability can be obtained.

On the other hand, even if a maleimide compound having optical transparency is used, polymerization will not proceed unless the photopolymerization initiator absorbs light with a wavelength of 405 nm (h-line) to generate radicals. However, the later-described photo-curing initiator according to the present embodiment has an absorbance of 0.1 or more at a wavelength of 405 nm (h-line), exhibiting extremely excellent absorbency with respect to light with a wavelength of 405 nm (h-line).

Since the maleimide compound (A) has excellent light transmittance as described above, even when light with a wavelength of 405 nm is used, the light sufficiently reaches the photocuring initiator, and radicals generated from the photocuring initiator As the reaction progresses, even a composition containing a large amount of the maleimide compound (A) can be photocured. According to this embodiment, homopolymerization of the maleimide compound (A) is also possible.
A cured product obtained by including the resin composition of the present embodiment is excellent in photocurability, heat resistance, and thermal stability, so that a protective film and an insulating layer can be suitably formed.

In general formula (1), n (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent photocurability.

In the resin composition of the present embodiment, the content of the maleimide compound (A) is not particularly limited. From the viewpoint of improving the more preferably 90 to 99.7 parts by mass.

In addition, the content of the maleimide compound (A) in the resin composition of the present embodiment is not particularly limited, but it is possible to obtain a cured product containing the maleimide compound as a main component, and it has photocurability, heat resistance, and thermal stability. From the viewpoint of improving the properties, it is preferably 40 to 100 parts by mass, more preferably 50 to 90 parts by mass, and 60 to 80 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. Part is more preferred. When the content of the maleimide compound (A) in the resin composition is 100 parts by mass, it means that the resin content is only the maleimide compound (A) and that it is a homopolymer of the maleimide compound (A).

As the maleimide compound (A), a commercially available product can be used. K-I Kasei Co., Ltd. BMI-650P (trade name, n = 8.8 (average) in the general formula (1)), K-I Kasei Co., Ltd. BMI-250P (trade name, general n = 3 to 8 (average) in formula (1)), CUA-4 (trade name, n = 1 in general formula (1)) manufactured by K.I. Kasei Co., Ltd., and the like.
These may be used singly or in admixture of two or more.

<Photocuring initiator (B)>
The photocuring initiator (B) (also referred to as component (B)) used in the present embodiment is not particularly limited as long as it has an absorbance of 0.1 or more at a wavelength of 405 nm (h-line), and is generally a photocurable resin composition. can be used.
Here, the absorbance at a wavelength of 405 nm (h-line) is 0.1 or more means that a chloroform solution containing 0.01% by mass of the component (B) is prepared, and a light beam with a wavelength of 405 nm (h-line) is used. It means that the absorbance is 0.1 or more when the absorbance of this chloroform solution is measured.

As the photo-curing initiator (B), the compound represented by the general formula (2) is preferred. For the compound represented by the general formula (2), a chloroform solution containing 0.01% by mass of this compound is prepared, and the absorbance of this chloroform solution is measured using light with a wavelength of 405 nm (h line). In addition, the absorbance is 0.1 or more, showing very excellent absorption for light with a wavelength of 405 nm (h-line). Therefore, this compound suitably generates radicals with respect to light with a wavelength of 405 nm (h-line).

The absorbance is preferably 0.2 or more. Although the upper limit is not particularly limited, it is 2.0, for example.

In the general formula (2), a plurality of R ₁ each independently represents a substituent or a phenyl group represented by the general formula (3). At least one of the plurality of R ₁ is preferably a substituent represented by the general formula (3).
In general formula (3), each of the plurality of R ₂ independently represents a hydrogen atom or a methyl group. At least one of the plurality of R ₂ is preferably a methyl group, and more preferably all are methyl groups.

Examples of the compound represented by the general formula (2) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, ethoxyphenyl Acylphosphine oxides such as (2,4,6-trimethylbenzoyl)-phosphine oxide can be mentioned. These may be used singly or in admixture of two or more.

Acylphosphine oxides exhibit very excellent absorption of active energy rays including a wavelength of 405 nm (h-line), and can favorably radically polymerize the maleimide compound (A). Therefore, according to the present embodiment, particularly when used in a multilayer printed wiring board, a resin composition that is excellent in photocurability, heat resistance and thermal stability, a resin sheet with a support, and a multilayer printed wiring board using them , a semiconductor device can be suitably manufactured.

In the resin composition of the present embodiment, the content of the photocuring initiator (B) is not particularly limited. , From the viewpoint of improving heat resistance, it is preferably 0.1 to 50 parts by weight with respect to a total of 100 parts by weight of the maleimide compound (A) and the photocuring initiator (B), and 0.2 to 30 parts by weight. It is more preferably 0.3 to 10 parts by mass.

The photo- curing initiator (B) can also use a commercial product, for example, Omnirad (registered trademark) 819 manufactured by IGM Resins, Omnirad (registered trademark) TPO G manufactured by IGM Resins, Omnirad (registered trademark) manufactured by IGM Resins (trademark) TPO LG and the like.

<Maleimide compound (C) other than maleimide compound (A) represented by general formula (1)>
In the resin composition of the present embodiment, when exposed to an active energy ray containing a wavelength of 405 nm (h-line), the resin composition of the present embodiment is photosensitized and photocured, as long as the general formula (1) A maleimide compound (C) (also referred to as component (C)) other than the represented maleimide compound (A) can be used. The maleimide compound (C) is described below.

The maleimide compound (C) used in the present embodiment is other than the maleimide compound (A) represented by the general formula (1), and is particularly limited as long as it is a compound having one or more maleimide groups in the molecule. isn't it. Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, fluorescein-5-maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3 ,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o- Phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy )-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimidoethane, 1,4- Bismaleimidobutane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,8-bismaleimido-3,6-dioxaoctane, 1,11-bis Maleimido-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide , 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy ) phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citracone imidophenyl)methane, polyphenylmethane maleimide, a maleimide compound represented by the following formula (4), a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6) A maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), a prepolymer of these maleimide compounds, or a prepolymer of a maleimide compound and an amine compound. .

As the maleimide compound represented by the following formula (4), a commercially available product can be used, for example, BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.). As the maleimide compound represented by the following formula (5), a commercially available product can be used, for example, MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.). As the maleimide compound represented by the following formula (6), a commercially available product can be used, for example, BMI-1500 (manufactured by Designer Molecules Inc. (DMI)). As the maleimide compound represented by the following formula (7), a commercially available product can be used, for example, BMI-1700 (manufactured by Designer Molecules Inc. (DMI)). As the maleimide compound represented by the following formula (8), commercially available products can be used, and examples include BMI-3000, BMI-5000, and BMI-9000 (all manufactured by Designer Molecules Inc. (DMI)). be done.

In formula (4), a plurality of R ₃ each independently represents a hydrogen atom or a methyl group. n ₁ represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5.

In formula (5), a plurality of R ₄ each independently represents a hydrogen atom or a methyl group. n ₂ represents an integer of 1 or more, preferably an integer of 1-5.

In formula (6), n ₃ represents an integer of 1 or more, preferably an integer of 1-10.

In formula (7), n ₄ represents an integer of 1 or more, preferably an integer of 1-10.

In formula (8), n ₅ represents an integer of 1 or more, preferably an integer of 1-10.

These maleimide compounds (C) can be used singly or in admixture of two or more.

The content of the maleimide compound (C) is not particularly limited, but when the maleimide compound (C) is used, it is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Filler (D)>
A filler (D) (also referred to as component (D)) can be used in combination with the resin composition of the present embodiment in order to improve various properties such as coating properties and heat resistance. The filler (D) used in the present embodiment is not particularly limited as long as it has insulating properties and does not inhibit the transparency to a wavelength of 405 nm (h-line). For example, silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum Compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica (mica), glass (e.g., short fibers) glass, spherical glass, fine powder glass (e.g., E glass, T glass, D glass, etc.), silicone powder, fluororesin filler, urethane resin filler, (meth)acrylic resin filler, polyethylene fillers, styrene-butadiene rubbers and silicone rubbers.

Among them, from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, (meth)acrylic resin filler, polyethylene filler, styrene-butadiene rubber and silicone rubber It is preferable that it is one or more selected.
These fillers (D) may be surface-treated with a silane coupling agent or the like, which will be described later.

Silica is preferable, and fused silica is more preferable, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties. Specific examples of silica include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Co., Ltd., and the like.
These fillers (D) can be used singly or in admixture of two or more.

Although the particle size of the filler is not particularly limited, it is usually 0.005 to 10 μm, preferably 0.01 to 1.0 μm, from the viewpoint of the ultraviolet light transmittance of the resin composition.

The content of the filler (D) is not particularly limited, but from the viewpoint of improving the ultraviolet light transmittance of the resin composition and the heat resistance of the cured product, 100 parts by mass of the resin solid content in the resin composition On the other hand, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and most preferably 10 parts by mass or less. When the filler (D) is contained, the lower limit is not particularly limited. It is usually 1 part by mass per part by mass.

<Silane coupling agent and wetting and dispersing agent>
In order to improve the dispersibility of the filler and the adhesive strength between the polymer and/or resin and the filler, the resin composition of the present embodiment may be used in combination with a silane coupling agent and/or a wetting and dispersing agent. It is possible.
These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; and epoxysilanes such as γ-glycidoxypropyltrimethoxysilane. (meth)acrylsilanes such as γ-(meth)acryloxypropyltrimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; Examples include phenylsilane-based silane coupling agents. These silane coupling agents can be used singly or in combination of two or more.

The content of the silane coupling agent in the resin composition of the present embodiment is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK (registered trademark)-W996, W9010, W903 manufactured by Big Chemie Japan Co., Ltd. Wetting and dispersing agents. . These wetting and dispersing agents can be used singly or in combination of two or more.
In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

<Cyanate ester compound, phenolic resin, oxetane resin, benzoxazine compound, epoxy resin and other compounds>
In the present embodiment, when exposed to an active energy ray containing a wavelength of 405 nm (h-line), the resin composition of the present embodiment is exposed to light, as long as the cured product is flame retardant and heat resistant. Various types of compounds and resins can be used, such as cyanate ester compounds, phenolic resins, oxetane resins, benzoxazine compounds, epoxy resins and other compounds, depending on properties such as and thermal expansion properties. For example, when heat resistance is required, cyanate ester compounds, benzoxazine compounds, and the like can be used, and phenol resins, oxetane resins, and the like can also be used.

These may be used singly or in admixture of two or more.

<Cyanate ester compound>
The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanato group (cyanate ester group) in the molecule.

For example, those represented by the general formula (9) can be mentioned.

In formula (9), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are more than one, they may be the same or different. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. Indicates a group to which an aryl group is attached. The aromatic ring in Ra may have a substituent, and the substituents in Ar ₁ and Ra can be selected at arbitrary positions. p represents the number of cyanato groups bonded to Ar ₁ and each independently represents an integer of 1-3. q represents the number of Ra atoms bonded to Ar ₁ , and is 4-p when Ar ₁ is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are single bonded. . t represents the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds with different t. When there are a plurality of X, each independently a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent nitrogen group having 1 to 10 Organic group (for example -NRN- (where R represents an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group ( -OC(=O)O-), a sulfonyl group (-SO ₂ -), a divalent sulfur atom or a divalent oxygen atom.

The alkyl group for Ra in general formula (9) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group, etc.).
Further, the hydrogen atom in the alkyl group in the general formula (9) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. good too.

Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl and 2,2-dimethylpropyl. group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of aryl groups include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl and trifluorophenyl. groups, methoxyphenyl groups, o-, m- or p-tolyl groups, and the like. Further examples of alkoxyl groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups.

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of the general formula (9) include methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylyl methylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like. A hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the general formula (9) include an imino group and a polyimide group.

Further, examples of the organic group for X in general formula (9) include those having structures represented by the following general formula (10) or the following general formula (11).

In formula (10), Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different. Rb, Rc, Rf, and Rg are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl having at least one phenolic hydroxy group indicates a group. Rd and Re are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group. . u represents an integer of 0 to 5;

In formula (11), Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, or an aryl group substituted with at least one cyanato group. Although v represents an integer of 0 to 5, it may be a mixture of compounds with different v.

Further, X in general formula (9) includes a divalent group represented by the following formula.

Here, z represents an integer of 4-7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of Ar ₂ in general formula (10) and Ar ₃ in general formula (11) include two carbon atoms represented by general formula (10) or two oxygen atoms represented by general formula (11). , a benzenetetrayl group bonded to the 1,4-positions or the 1,3-positions, the two carbon atoms or two oxygen atoms being 4,4′-positions, 2,4′-positions, 2,2′-positions, 2 , 3′-position, 3,3′-position, or 3,4′-position, and a biphenyltetrayl group bound to the 3,4′-position, and the two carbon atoms or two oxygen atoms are 2,6-position, 1,5-position, , 1,6-positions, 1,8-positions, 1,3-positions, 1,4-positions, or 2,7-positions.
The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg in general formula (10) and Ri and Rj in general formula (11) are the same as those in general formula (9).

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (9) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- (4-cyanaphenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1- Cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2 - methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato -4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2, 6-di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4- dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3-,1,4-,1,5-,1,6-,1,7-,2,3-,2,6- or 2,7-dicyanatocinaphthalene, 2,2′- or 4,4'-di anatobiphenyl, 4,4′-dicyanatooctafluorobiphenyl, 2,4′- or 4,4′-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,1-bis( 4-cyanatophenyl)ethane, 1,1-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanato-3-methylphenyl ) propane, 2,2-bis(2-cyanato-5-biphenylyl)propane, 2,2-bis(4-cyanatophenyl)hexafluoropropane, 2,2-bis(4-cyanato-3,5- dimethylphenyl)propane, 1,1-bis(4-cyanatophenyl)butane, 1,1-bis(4-cyanatophenyl)isobutane, 1,1-bis(4-cyanatophenyl)pentane, 1,1 -bis(4-cyanatophenyl)-3-methylbutane, 1,1-bis(4-cyanatophenyl)-2-methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane , 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)pentane, 2,2-bis(4-cyanatophenyl)hexane, 2,2-bis(4 -cyanatophenyl)-3-methylbutane, 2,2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3, 3-bis(4-cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3,3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanato phenyl)-2-methylpentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylpentane, 4,4- Bis(4-cyanatophenyl)-3-methylheptane, 3,3-bis(4-cyanatophenyl)-2-methylheptane, 3,3-bis(4-cyanatophenyl)-2,2-dimethyl Hexane, 3,3-bis(4-cyanatophenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,2,4-trimethylpentane, 2,2-bis( 4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanatophenyl)phenylmethane, 1,1-bis(4-cyanatophenyl)-1-phenyl ethane, bis(4 -cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato-3-isopropyl phenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis(4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2,2-dichloroethylene, 1,3 -bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4- anatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl)methyl]biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis(4-cyanatophenyl)-2 - propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester ( 4-cyanatophenyl-4-cyanatobenzoate), bis-(4-cyanatophenyl)carbonate, 1,3-bis(4-cyanatophenyl)adamantane, 1,3-bis(4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis(4-cyanatophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methyl Phenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9′-bis(4-cyanatophenyl)fluorene, 9,9-bis(4-cyanato-3-methylphenyl ) fluorene, 9,9-bis(2-cyanato-5-biphenylyl)fluorene, tris(4-cyanatophenyl)methane, 1,1,1-tris(4-cyanatophenyl)ethane, 1,1, 3-tris(4-cyanatophenyl)propane, α,α,α'-tris(4-cyanatophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4- anatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N-methyl- 4-cyanatoanilino)-6-(N-methylanilino no)-1,3,5-triazine, bis(N-4-cyanato-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanato-4-methylphenyl)-4, 4'-oxydiphthalimide, bis(N-4-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroisopropyl lidene)diphthalimide, tris(3,5-dimethyl-4-cyanatobenzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyanatophenyl)phthalimidine, 2-(4-methylphenyl)-3 , 3-bis(4-cyanatophenyl)phthalimidine, 2-phenyl-3,3-bis(4-cyanato-3-methylphenyl)phthalimidine, 1-methyl-3,3-bis(4-cyanatophenyl) Indolin-2-one and 2-phenyl-3,3-bis(4-cyanatophenyl)indolin-2-one.

These cyanate ester compounds can be used singly or in combination of two or more.

Further, as another specific example of the cyanate ester compound represented by the general formula (9), phenol novolac resin and cresol novolac resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin or Formaldehyde compound such as paraformaldehyde reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9 ,9-bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (Ar ₄ —(CH ₂ Y) ₂ (Ar ₄ represents a phenyl group and Y represents a halogen atom; the same shall apply hereinafter in this paragraph) by reacting a bishalogenomethyl compound represented by phenolic compound with an acidic catalyst or without a catalyst. a product obtained by reacting a bis(alkoxymethyl) compound represented by Ar ₄ —(CH ₂ OR) ₂ (R represents an alkyl group) with a phenol compound in the presence of an acidic catalyst; Alternatively, a bis(hydroxymethyl) compound represented by Ar ₄ —(CH ₂ OH) ₂ and a phenolic compound are reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenolic compound. polycondensation), phenol-modified xylene formaldehyde resin (by a known method, a xylene formaldehyde resin and a phenolic compound are reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (by a known method, Naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (by a known method, one phenolic hydroxy group is Polyhydric hydroxynaphthalene compounds having two or more molecules in the molecule are dehydrated and condensed in the presence of a basic catalyst), etc., cyanated by the same method as above, and prepolymers thereof etc. These are not particularly limited. These cyanate ester compounds can be used singly or in combination of two or more.

Methods for producing these cyanate ester compounds are not particularly limited, and known methods can be used. An example of such a production method includes obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known technique to form a cyanate. Methods for cyanating a hydroxy group include, for example, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

Resin cured products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

Although the content of the cyanate ester compound is not particularly limited, it is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Phenolic resin>
As the phenolic resin, generally known phenolic resins having two or more hydroxyl groups in one molecule can be used. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl-type phenolic resins, cresol novolac-type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolak resins, polyfunctional naphthol resins, anthracene-type phenolic resins, naphthalene skeleton-modified novolac-type phenolic resins, phenol aralkyl-type phenolic resins, naphthol aralkyl-type phenolic resins Phenol resins, dicyclopentadiene type phenol resins, biphenyl type phenol resins, alicyclic phenol resins, polyol type phenol resins, phosphorus-containing phenol resins, polymerizable unsaturated hydrocarbon group-containing phenol resins, hydroxyl group-containing silicone resins, and the like. but is not particularly limited. These phenol resins can be used singly or in admixture of two or more.

The content of the phenol resin is not particularly limited, and is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Oxetane resin>
Commonly known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoro methyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toagosei, trade name), OXT-121 (manufactured by Toagosei, trade name) etc., and is not particularly limited. These may be used singly or in admixture of two or more.

The content of the oxetane resin is not particularly limited, and is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Benzoxazine compound>
As the benzoxazine compound, generally known compounds can be used as long as they are compounds having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical, trade name), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical, trade name), bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical, trade name) ), phenolphthalein-type benzoxazine, etc., but are not particularly limited. These may be used singly or in admixture of two or more.

The content of the benzoxazine compound is not particularly limited, and is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Epoxy resin>
Epoxy resins are not particularly limited, and generally known ones can be used. For example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin , Tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin Epoxy resins, aralkyl novolak type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds obtained by epoxidizing double bonds such as butadiene, hydroxyl group-containing silicones Compounds obtained by reacting resins with epichlorohydrin, and halides thereof.

Examples of naphthalene-type epoxy resins include resins represented by the following formula (12). As the epoxy resin, a commercially available product can be used, and HP-4710 (trade name) manufactured by DIC Corporation can be mentioned.

These epoxy resins can be used singly or in admixture of two or more.

Although the content of the epoxy resin is not particularly limited, it is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Other compounds>
Other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether and ethylene glycol divinyl ether, styrenes such as styrene, methylstyrene, ethylstyrene and divinylbenzene, triallyl isocyanurate and trimethallyl isocyanurate. , bisallyl nadimide and the like. These may be used singly or in admixture of two or more.
The content of the other compound is not particularly limited, but is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<Organic solvent>
The resin composition of the present embodiment may contain a solvent, if necessary. For example, if an organic solvent is used, the viscosity during preparation of the resin composition can be adjusted. The type of solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition. Specific examples thereof include, but are not limited to, ketones such as acetone, methyl ethyl ketone and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate. is mentioned.
These organic solvents can be used singly or in admixture of two or more.

<Other ingredients>
In the resin composition of the present embodiment, various polymer compounds such as thermosetting resins, thermoplastic resins and their oligomers, elastomers, etc. that have not been mentioned so far are included as long as the characteristics of the present embodiment are not impaired. flame-retardant compounds not mentioned heretofore; additives and the like can also be used in combination. These are not particularly limited as long as they are commonly used. Examples of flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates. Additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface modifiers, brighteners, polymerization inhibitors, thermosetting Accelerators and the like. These components can be used singly or in admixture of two or more.
In the resin composition of the present embodiment, the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

<Method for producing resin composition>
The resin composition of the present embodiment comprises the maleimide compound (A) represented by the general formula (1), the photo-curing initiator (B), and, if necessary, the maleimide represented by the general formula (1). It is prepared by appropriately mixing a maleimide compound (C) other than the compound (A), a filler (D), other resins, other compounds, additives, and the like. The resin composition of this embodiment can be suitably used as a varnish for producing a resin sheet of this embodiment, which will be described later.

The method for producing the resin composition of the present embodiment is not particularly limited, and includes, for example, a method in which the respective components described above are sequentially blended in a solvent and sufficiently stirred.

During the production of the resin composition, known treatments (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed as necessary. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. The stirring, mixing, and kneading processes include, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as three rolls, a ball mill, a bead mill, and a sand mill, or a revolving or rotating type It can be appropriately carried out using a known device such as a mixing device. In addition, an organic solvent can be used as necessary during the preparation of the resin composition of the present embodiment. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

<Application>
The resin composition of the present embodiment can be used for applications that require an insulating resin composition, and is not particularly limited. Insulating resin sheets such as photosensitive films, photosensitive films with a support, and prepregs , circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-embedding resins, and the like. Among others, it can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board or as a solder resist.

<Resin sheet>
The resin sheet of the present embodiment comprises a support and a resin layer containing the resin composition of the present embodiment arranged on the surface of the support, and a support obtained by applying a resin composition to one or both sides of the support. It is a body-attached resin sheet. A resin sheet can be produced by coating a resin composition on a support and drying the resin composition.

The support used in the resin sheet of the present embodiment is not particularly limited, but a known support can be used, preferably a resin film. Examples of resin films include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol. Resin films such as films and triacetyl acetate films can be used. Among them, a PET film is preferable.

For the resin film, a film coated with a release agent on the surface can be preferably used in order to facilitate separation from the resin layer. The thickness of the resin film is preferably in the range of 5-100 μm, more preferably in the range of 10-50 μm. When the thickness is less than 5 μm, the support tends to be torn when the support is peeled off before development. be.

In order to reduce scattering of light during exposure, the resin film preferably has excellent transparency.

Furthermore, in the resin sheet of the present embodiment, the resin layer may be protected with a protective film.
By protecting the resin layer side with a protective film, it is possible to prevent dust from adhering to the surface of the resin layer and scratches on the surface of the resin layer. As the protective film, a film made of the same material as the resin film can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 to 50 μm, more preferably in the range of 5 to 40 μm. If the thickness is less than 1 μm, the protective film tends to be difficult to handle, and if it exceeds 50 μm, it tends to be inexpensive. The protective film preferably has a lower adhesive strength between the resin layer and the protective film than the adhesive strength between the resin layer and the support.

The method for producing the resin sheet of the present embodiment is not particularly limited. For example, the resin sheet is produced by applying the resin composition of the present embodiment to a support such as a PET film and removing the organic solvent by drying. and the like.
The coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater and the like. The drying can be carried out, for example, by heating in a dryer at 60 to 200° C. for 1 to 60 minutes.

From the viewpoint of preventing diffusion of the organic solvent in the subsequent steps, the amount of the residual organic solvent in the resin layer is preferably 5% by mass or less with respect to the total mass of the resin layer. The thickness of the resin layer is preferably 1 to 50 μm from the viewpoint of improving handleability.

The resin sheet of this embodiment can be used as an insulating layer of a multilayer printed wiring board.

<Multilayer printed wiring board>
The multilayer printed wiring board of the present embodiment includes an insulating layer containing the resin composition of the present embodiment, and can be obtained, for example, by stacking one or more of the above resin sheets and curing. Specifically, it can be produced by the following method.

(Lamination process)
The resin layer side of the resin sheet of this embodiment is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of circuit substrates include glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the printed wiring board is a patterned conductor layer (circuit) is also referred to here. included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like. In the lamination step, when the resin sheet has a protective film, the protective film is peeled off, and then the resin sheet and the circuit board are preheated as necessary, and the circuit board is laminated while pressing and heating the resin layer. crimp to. In the resin sheet of the present embodiment, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination step are not particularly limited, but for example, the crimping temperature (laminating temperature) is preferably 50 to 140° C., the crimping pressure is preferably 1 to 15 kgf/cm ² , and the crimping time is preferably 5. It is preferable to laminate under a reduced pressure of 20 mmHg or less for 300 seconds. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd., and the like.

(Exposure process)
After the resin sheet is provided on the circuit board by the lamination process, a predetermined portion of the resin layer is irradiated with an active energy ray containing a wavelength of 405 nm (h-line) as a light source, and an exposure step of curing the resin layer in the irradiated portion. conduct. The irradiation may be performed through a mask pattern, or a direct writing method for direct irradiation may be used.

The dose of active energy rays containing a wavelength of 405 nm (h-line) is about 10 to 10,000 mJ/cm ² . The method of exposing through a mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which a parallel light beam is used for exposure without close contact. I don't mind. Further, when a support exists on the resin layer, exposure may be performed from above the support, or exposure may be performed after peeling off the support.

(Development process)
After the exposure step, if there is a support on the resin layer, the support is removed, and then wet development is performed to remove the portion that has not been photocured (unexposed portion). A pattern of insulating layers can be formed.

In the case of the wet development, the developer is not particularly limited as long as it selectively dissolves the unexposed portion, but a developer such as an organic solvent is used. In this embodiment, the development step using an organic solvent is particularly preferred. These developers can be used alone or in combination of two or more. Moreover, as a developing method, for example, known methods such as spraying, rocking immersion, brushing, and scraping can be used.

In the pattern formation of this embodiment, two or more of the above-described developing methods may be used in combination, if necessary. Methods of development include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, slapping, etc., and the high-pressure spray method is suitable for improving resolution. A spray pressure of 0.02 to 0.5 MPa is preferable when a spray method is employed.

(Post-baking process)
After completion of the developing process, a post-baking process is performed to form an insulating layer (cured product). Examples of the post-baking process include an ultraviolet irradiation process using a high-pressure mercury lamp, a heating process using a clean oven, and the like, and these processes can be used in combination. In the case of irradiating with ultraviolet rays, the irradiation dose can be adjusted as necessary, for example, the irradiation can be carried out at an irradiation dose of about 0.05 to 10 J/cm ² . The heating conditions can be appropriately selected as necessary, preferably in the range of 150 to 220° C. for 20 to 180 minutes, more preferably in the range of 160 to 200° C. and 30 to 150 minutes.

(Conductor layer forming step)
Next, a conductor layer is formed on the surface of the insulating layer by dry plating. As dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and heating and evaporating the metal. In the sputtering method, for example, the support is placed in a vacuum chamber, an inert gas such as argon is introduced, a DC voltage is applied, and the ionized inert gas collides with the target metal. A metal film can be formed on the insulating layer.

Next, a conductor layer is formed by electroless plating, electrolytic plating, or the like. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like can be used.

<Semiconductor device>
The semiconductor device of this embodiment includes an insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board of the present embodiment. Here, the conductive portion is a portion of the multilayer printed wiring board that transmits an electric signal, and the portion may be a surface or an embedded portion. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a bare buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like.

A semiconductor device can also be manufactured by forming an insulating layer containing the resin composition of the present embodiment on a semiconductor chip or a substrate on which a semiconductor chip is mounted. The shape of the substrate on which the semiconductor chips are mounted may be wafer-like or panel-like. After formation, it can be manufactured using the same method as the multilayer printed wiring board described above.

[Transmittance of maleimide compound and absorbance of photocuring initiator at wavelength 405 nm (h-line)]
As the maleimide compound (A) represented by the general formula (1), BMI-1000P (trade name) manufactured by K.I. Kasei Co., Ltd. (n in formula (1) is 13.6 (average value); Mw) uses 1338) to prepare a chloroform solution containing 0.01% by mass of this BMI-1000P (trade name), and a UV-vis measurement device (Hitachi High Technologies Hitachi spectrophotometer U-4100). was used to measure transmittance at a wavelength of 405 nm.
Similarly, as the maleimide compound (A) represented by the general formula (1), BMI-650P (trade name) manufactured by K.I Kasei Co., Ltd. (n in formula (1) is 8.8 (average value), Mass average molecular weight (Mw) is 1065) and BMI-250P (trade name) manufactured by K.I. Kasei Co., Ltd. (n in formula (1) is 3 to 8 (average value), mass average molecular weight (Mw) is 500 to 1500) was used to measure transmittance at a wavelength of 405 nm.
Similarly, a maleimide compound (BMI2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used to measure transmittance at a wavelength of 405 nm.

Similarly, 0.01% by mass of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (OMNIRAD (registered trademark) 819 manufactured by IGM Resins) is contained as a photocuring initiator (B). Absorbance was measured at a wavelength of 405 nm for the chloroform solution.
Similarly, as photoinitiators, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (OMnirad® 369 from IGM Resins) and 2-methyl-1- Absorbance was measured at a wavelength of 405 nm using [4-(methylthio)phenyl]-2-morpholinopropan-1-one (OMNIRAD (registered trademark) 907 manufactured by IGM Resins).
Table 1 shows the results.

[Example 1]
(Preparation of resin composition and resin sheet)
90 parts by mass of a maleimide compound (A) (BMI-1000P (trade name)) represented by the general formula (1) and 2,4,6-trimethylbenzoyl-diphenyl-phosphine as a photocuring initiator (B) 10 parts by mass of oxide (Omnirad (registered trademark) 819) was mixed and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). This varnish is applied onto a 38 μm thick PET film (Unipeel (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). Then, it was dried by heating at 80° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin layer having a thickness of 30 μm.

(Creation of inner layer circuit board)
Glass cloth substrate BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, thickness 0.2 mm, CCL (registered trademark)-HL832NS manufactured by Mitsubishi Gas Chemical Co., Ltd.) with an inner layer circuit formed The surface of the copper was roughened by CZ8100 manufactured by the company, and an inner layer circuit board was obtained.

(Preparation of laminate for evaluation)
The resin surface of the resin sheet is placed on the inner layer circuit board, and a vacuum laminator (manufactured by Nikko Materials Co., Ltd.) is used to vacuum for 30 seconds (5.0 MPa or less), and then the pressure is 10 kgf / cm. ^2. Lamination molding was performed at a temperature of 70°C for 30 seconds. Further, lamination molding was performed at a pressure of 10 kgf/cm ² and a temperature of 70° C. for 60 seconds to obtain a laminated body in which the inner layer circuit board, the resin layer and the support were laminated.

[Example 2]
The amount of maleimide compound (A) (BMI-1000P (trade name)) was changed from 90 parts by mass to 70 parts by mass, and the amount of photocuring initiator (B) ( Omnirad (registered trademark) 819) was changed to 10 parts by mass. A resin sheet was obtained in the same manner as in Example 1, except that 30 parts by mass was used instead of 1 part. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Example 3]
A resin sheet was obtained in the same manner as in Example 1, except that 90 parts by mass of BMI-650P (trade name) was used as the maleimide compound (A) instead of BMI-1000P (trade name). Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Example 4]
A resin sheet was obtained in the same manner as in Example 1, except that 90 parts by mass of BMI-250P (trade name) was used as the maleimide compound (A) instead of BMI-1000P (trade name). Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Comparative Example 1]
A resin sheet was obtained in the same manner as in Example 1, except that 90 parts by mass of a maleimide compound (BMI2300 (trade name)) was used instead of the maleimide compound (A) (BMI-1000P (trade name)). Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation.

[Comparative Example 2]
A resin sheet was obtained in the same manner as in Example 1, except that 10 parts by mass of Omnirad (registered trademark) 369 was used instead of Omnirad (registered trademark) 819 as a photocuring initiator. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation.

[Comparative Example 3]
A resin sheet was obtained in the same manner as in Example 1, except that 10 parts by mass of Omnirad (registered trademark) 907 was used instead of Omnirad (registered trademark) 819 as a photocuring initiator. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation.

[Comparative Example 4]
TrisP-PA (propylene glycol monomethyl ether acetate of epoxy acrylate compound) solution (KAYARAD (registered trademark) ZCR-6007H manufactured by Nippon Kayaku Co., Ltd., nonvolatile content 65% by mass, acid value: 70 mgKOH/g) was 116.9. Parts by mass (76 parts by mass in terms of non-volatile content), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.) 16 parts by mass, and Omnirad (registered as a photocuring initiator (B) Trademark) 819 was mixed with 8 parts by mass and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). This varnish is applied onto a PET film having a thickness of 38 μm (Unipeel (registered trademark) TR1-38 (trade name) manufactured by Unitika Ltd.) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). Then, it was dried by heating at 80° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin layer having a thickness of 30 μm. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Comparative Example 5]
Bisphenol F type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H manufactured by Nippon Kayaku Co., Ltd., nonvolatile content 68% by mass, acid value: 70 mgKOH / g) 105.9 parts by mass (72 parts by mass in terms of nonvolatile content ), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.) 19 parts by weight, and Omnirad (registered trademark) 819 as a photocuring initiator (B) 9 parts by weight. and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). This varnish is applied onto a PET film having a thickness of 38 μm (Unipeel (registered trademark) TR1-38 (trade name) manufactured by Unitika Ltd.) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). Then, it was dried by heating at 80° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin layer having a thickness of 30 μm. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Physical property measurement evaluation]
The laminate for evaluation and the cured product for evaluation were measured and evaluated by the following methods. Those results are shown in Table 1.

<Photocurability>
Photo DSC (T.A. Instruments Japan Co., Ltd.) equipped with a light source (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvix Co., Ltd.) capable of irradiating active energy rays including a wavelength of 405 nm (h-line) DSC-2500 (trade name)), the obtained laminate for evaluation was irradiated with an illuminance of 30 mW and an exposure time of 3.5 minutes, and the horizontal axis was time (sec) and the vertical axis was heat flow (mW). got the graph. The enthalpy (J/g) was defined as the peak area when a horizontal line was drawn from the end point of this graph. The curability was evaluated by enthalpy, and 1 (J/g) or more was evaluated as "◯", and less than 1 (J/g) as "x".

<Heat resistance (glass transition temperature)>
The resin sheet cured in the photocurability test was further subjected to a post-baking step of heat treatment at 180° C. for 120 minutes, and then the support was peeled off to obtain a cured product for evaluation.
This cured product for evaluation was heated at 10° C./min using a DMA device (dynamic viscoelasticity measuring device DMAQ800 (trade name) manufactured by TA Instruments), and the loss modulus peak position was measured at the glass transition temperature (Tg, °C).

<Thermal stability>
Using a simultaneous differential thermogravimetric measurement device (TG-DTA6200 (trade name)), at the measurement start temperature (20 ° C), the temperature increase rate (10 ° C / min), and the target temperature (500 ° C), in the photocuring test As a result, the temperature at which the weight loss rate of the cured product for evaluation became 5% was defined as thermal stability (°C).

As is clear from Table 2, the resin composition of the present embodiment is photosensitized and can be photocured when exposed to active energy rays having a wavelength of 405 nm (h-line).

Claims (5)

a maleimide compound (A) represented by the following general formula (1);
A chloroform solution containing 0.01% by mass of the photocuring initiator (B) is prepared, and the absorbance of this chloroform solution is measured using a light beam with a wavelength of 405 nm (h line), and the absorbance is 0.1 or more. and the photocuring initiator (B) which is
The photocuring initiator (B) is a compound represented by the following general formula (2),
The content of the maleimide compound (A) is 40 to 100 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition,
The content of the maleimide compound (A) is 50 to 99.9 parts by mass with respect to a total of 100 parts by mass of the maleimide compound (A) and the photocuring initiator (B),
The content of the photocuring initiator (B) is 0.1 to 50 parts by mass with respect to a total of 100 parts by mass of the maleimide compound (A) and the photocuring initiator (B).
Resin composition.

(In formula (1), the number of n is 1 to 21. ).

(In formula (2), each R ₁ independently represents a substituent represented by the following general formula (3) or a phenyl group.).

(In formula (3), -* represents a bond, and each R ₂ independently represents a hydrogen atom or a methyl group). a support;
a resin layer arranged on one side or both sides of the support,
The resin layer contains the resin composition according to claim 1 ,
resin sheet. 3. The resin sheet according to claim 2 , wherein the resin layer has a thickness of 1 to 50 μm. A multilayer printed wiring board comprising the resin composition according to claim 1 . A semiconductor device comprising the resin composition according to claim 1 .